Spectroscopy of Intermolecular Field Interactions in Solutions

Lutskii, A. E.; Prezhdo, V. V.; Degtereva, L I; Gordienko, V. G.

doi:10.1070/rc1982v051n08abeh002917

Cited by 13 publications

(9 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[1][2][3][4][5][6][7][8][9][10][11] For this reason, vibrational line shape analyses, 5,10 and more recently time-domain measurements of vibrational relaxation and dephasing, 7,8 have been widely used to probe solvation forces. 12 While the basic theory of how intermolecular interactions affect vibrations is well established, understanding and predicting the static and especially the dynamic aspects of solute-solvent interactions in dense systems remains an active area of research.…”

Section: Introductionmentioning

confidence: 99%

“…MacPhail and co-workers analyzed the solvent dependence of these cyclohexane vibrations in both normal liquids 49 and in supercritical CO 2 38,39 using theoretical approaches developed by Schweizer and Chandler 52 and Ben-Amotz and Herschbach. 53 Both of these approaches partition the solute-solvent interactions into short-range repulsive contributions, which can be modeled with analytic hardsphere approximations, and longer-range attractive interactions, treated using a mean-field approach.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Molecular-dynamics simulations of solvent effects on the C–H stretching Raman bands of cyclohexane-d11 in supercritical CO2 and liquid solvents

Frankland

Maroncelli

1999

The Journal of Chemical Physics

View full text Add to dashboard Cite

Solvent-solute interactions and the Raman CH stretching spectrum of cyclohexane-d 11 . II. Density dependence in supercritical carbon dioxide Molecular-dynamics simulations are used to elucidate the molecular basis for the solvent effects on the isolated C-H stretching bands observed in the Raman spectrum of cyclohexane-d 11 . The main focus is on modeling the density dependence of the spectrum in supercritical CO 2 recently reported by Pan, McDonald, and MacPhail ͓J. Chem. Phys. 110, 1677 ͑1999͔͒, but several liquid solvents (CCl 4 , CS 2 , and CH 3 CN) have also been examined. The frequency shifts and line shapes of the Raman spectrum are simulated using a rigid solute and standard line shape theory in the limit of pure dephasing. Three models for the vibration-solvent coupling are considered. The simplest model, which is based on ground-state forces alone, provides a surprisingly good representation of the density dependence of the linewidths-line shapes but predicts the wrong sign for the gas-to-solution frequency shifts. This failure is due to the neglect of changes in bond polarizability upon vibrational excitation. Allowing for this polarizability difference via a semiempirical approach provides an accurate description of both the linewidths and frequency shifts with a physically reasonable vibrational difference potential. Interpretation of the instantaneous frequency shifts simulated with this model leads to the following general conclusions concerning the solvent effect on these spectra: ͑i͒ The relatively small gas-to-solution frequency shifts observed in experiment are the result of the near cancellation of much larger positive and negative contributions from repulsive and attractive interactions. ͑ii͒ Fluctuations in the instantaneous frequency are sufficiently fast ͑correlation times ϳ100 fs͒ that the spectra are homogeneously broadened in all solvents examined. ͑iii͒ The dynamics of the solvent-solute interactions that determine the Raman line shapes are quite well described by an isolated binary collision ͑''IBC''͒ type picture. ͑iv͒ The simplicity of the dynamics, and the success of this IBC description, is due at least in part to the special, localized character of these isolated C-H stretching modes. ͑v͒ The linear density dependence of the linewidths observed in supercritical CO 2 reflects the modest extent of local density augmentation in the cyclohexane-CO 2 system.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Molecular-dynamics simulations of solvent effects on the C–H stretching Raman bands of cyclohexane-d11 in supercritical CO2 and liquid solvents

Frankland

Maroncelli

1999

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…When absorption spectra are measured in solvents of different polarity, it is found that the positions, intensities, and shapes of the absorption bands are usually modified by these solvents . These changes are a result of physical intermolecular solute–solvent interaction forces (such as ion–dipole, dipole–dipole, dipole‐induced dipole, hydrogen bonding, etc.…”

Section: Resultsmentioning

confidence: 99%

“…), which above all tend to alter the energy difference between ground and excited state of the absorbing species containing the chromophore . Thus, solvent effects on absorption spectra can be used to provide information about solute‐solvent interactions . In contrast, when excited states of a molecule are created in solution by continuous or flash excitation, the excited‐state molecule interacts to a varying degree with the surrounding solvent molecules, depending on their polarity, before returning to the ground state.…”

Section: Resultsmentioning

confidence: 99%

Spectrofluorimetric determination of the antineoplastic agent lomustine based on the sensitizing effect of β‐cyclodextrin

2015

View full text Add to dashboard Cite

The effects of solvent dipolarity/polarizability and solvent-solute hydrogen bonding on the photophysical properties of the antineoplastic drug lomustine were analysed by means of the linear solvation energy relationship (LSER) concept proposed by Kamlet and Taft. The LSER method enabled the overall solvent effects to be quantitatively estimated and separated into specific and non-specific contributions. The molecular encapsulation of lomustine by β-cyclodextrin (β-CD) has been studied using fluorescence spectroscopy. The results are discussed in terms of the binding parameter and the effect of the solvent used. It was concluded that β-CD forms a 1:1 inclusional complex with lomustine in acetonitrile solution and its association constant was calculated to be 500 M(-1). In addition, and for the first time, a simple, rapid and high sensitive fluorimetric method for the determination of lomustine was developed based upon the enhancement effect produced through complex formation with β-CD. The new approach for the quantification of lomustine in the presence of β-CD was described in aqueous and organic solutions. Better limits of detection (0.31 µg ml(-1)) and quantification (1.05 µg ml(-1)) were obtained in aqueous solution with respect to those obtained in organic solvent.

show abstract

“…It is discussed from historical viewpoint, for example, in a recent book [24]. The dependences 9- (11) were proved on the spectral characteristics of molecules such as IR-spectra (Δ ν), NMRspectra (proton chemical shift, Δ δ H ), and electronic absorption spectra (E max , f) [25].…”

Section: Discrete-conttinuum Modelmentioning

confidence: 99%

Vapor-phase molar Kerr constant values from solution measurements

Prezhdo¹,

Olan²,

Prezhdo³

et al. 2015

Journal of Molecular Structure

View full text Add to dashboard Cite

A method is proposed for determination of molar Kerr constants (mK) by extrapolation of the values measured in a series of selected solvents. The mK values of 19 organic compounds were calculated. Most of the compounds cannot be studied in the vapour phase. The discrete-continuum solvation model was applied to investigate the influence of solvent nature on solubility of the compounds under investigation. It is shown that universal interactions between the solvent and solute molecules, including the dispersive, inductive, and dipole−dipole interactions, dominate the solvation process. The optimum model of internal field was chosen to determine the Kerr constant. The values of mK gas measured experimentally coincide with the values of ' 0 = α ϕ mK that were obtained by extrapolation of mK'. Hence, this method can be applied to calculate the values of molar Kerr constants on the basis of measurements in solutions.

show abstract

Spectroscopy of Intermolecular Field Interactions in Solutions

Cited by 13 publications

References 2 publications

Molecular-dynamics simulations of solvent effects on the C–H stretching Raman bands of cyclohexane-d11 in supercritical CO2 and liquid solvents

Molecular-dynamics simulations of solvent effects on the C–H stretching Raman bands of cyclohexane-d11 in supercritical CO2 and liquid solvents

Spectrofluorimetric determination of the antineoplastic agent lomustine based on the sensitizing effect of β‐cyclodextrin

Vapor-phase molar Kerr constant values from solution measurements

Contact Info

Product

Resources

About